CN103429566B - Method for preparing a dinitrile compound - Google Patents
Method for preparing a dinitrile compound Download PDFInfo
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- CN103429566B CN103429566B CN201280014212.4A CN201280014212A CN103429566B CN 103429566 B CN103429566 B CN 103429566B CN 201280014212 A CN201280014212 A CN 201280014212A CN 103429566 B CN103429566 B CN 103429566B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/02—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton
- C07C255/04—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and saturated carbon skeleton containing two cyano groups bound to the carbon skeleton
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
- B01J23/04—Alkali metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C255/00—Carboxylic acid nitriles
- C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
- C07C255/11—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton
- C07C255/13—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound oxygen atoms bound to the same saturated acyclic carbon skeleton containing cyano groups and etherified hydroxy groups bound to the carbon skeleton
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to a method for preparing a dinitrile compound. More particularly, the present invention relates to a method for preparing a dinitrile compound by reacting an alcohol compound with a nitrile compound having a carbon-carbon unsaturated bond at a terminal thereof under anhydrous conditions, wherein potassium alkoxide of C1-C5 is used as a catalyst during the reaction. According to the method of the present invention, good productivity is provided due to a short reaction time, and a high-purity dinitrile compound can be simply prepared.
Description
Technical field
The present invention relates to a kind of preparation method of dinitrile compound, and more specifically, be related to one kind and do not form any
The method that dinitrile compound can be simply prepared while impurity.
This application claims the Korean Patent of Application No. 10-2011-0024437 that on March 18th, 2011 is submitted in Korea
The priority of application, which includes this specification in full by reference.
The application also requires that the Korea of Application No. 10-2012-0003863 that on January 12nd, 2012 submitted in Korea is special
The priority of profit application, which includes this specification in full by reference.
Background technology
Energy storage technology causes increasing concern in recent years.As the application extension of energy storage technology is to mobile electricity
Words, video camera, notebook computer even electric automobile, the high-energy used for the power supply as this electronic equipment are close
The battery requirements of degree are improved.As the battery that disclosure satisfy that the needs, lithium secondary battery be considered as most it is promising simultaneously
And be just actively studied.
Many secondary cells are available at present.In these, in the lithium secondary battery of the exploitation nineties in morning up to 20th century
Typical example include：By made by can be embedded in the carbonaceous material with deintercalate lithium ions anode, made by lithium-containing oxides etc.
Into negative electrode and lithium salts the non-aqueous electrolytic solution in mixed organic solvents is dissolved in appropriate amount.
It is easy to electrolyte solution when the organic solvent long term storage at high temperature for non-aqueous electrolytic solution
Oxidation.The oxidation causes the generation of gas, and therefore cause cell expansion (swelling), ultimately result in the deterioration of battery.
Being decomposed the gas for causing by electrolyte solution can make the battery component deformation of bag (pouch) type or pot and induce internal short
Road.In extreme circumstances, batteries caught fire or blast may be made.The oxidation of electrolyte solution, by dissolving under high voltage condition
Transition metal and accelerate.
To solve the above problems, it has been suggested that various additives are preventing the swelling of non-aqueous electrolytic solution battery.This adds
Plus a kind of example of agent is the dinitrile compound with two or more ehter bond.Acted on known to dinitrile compound as follows：Suppress electrolysis
Oxidation between matter solution and negative electrode and suppress heating.Also, dinitrile compound also suppresses the oxidation Decomposition of electrolyte solution anti-
Answer and prevent the expansion of battery.
In the conventional method for preparing dinitrile compound, base catalyst such as alkali metal hydroxide or quaternary ammonium compound are used
Cyanoethylation reaction between alcoholic compound and acrylonitrile.Sodium hydroxide economy is most excellent and is readily synthesized, widely
It is known for use as base catalyst.
However, form cyanoethanol as water and the acrylonitrile reactor of medium in cyanoethylation reaction, which is again with third
Alkene nitrile reacts and forms double (2- cyano ethyls) ethers, thus there is which as impurity.
Attempt certain methods to suppress the formation of by-product, such as by controlling the amount of the acrylonitrile for consuming in the reaction,
And by controlling acrylonitrile concentration with the titration speed of slow acrylonitrile.However, these methods have some problems, such as
Residual content of alcoholic compound in the reactive mixture etc. is improved, this causes final product quality to reduce.
Another feasible method is, if reacted in anhydrous conditions, supposition can prevent from causing cyanogen by water
Ethylize.However, in this case, according to the presence of alkali metal hydroxide or organic base, there is the polyreaction of acrylonitrile,
This causes the discoloration of reactant.
On the other hand, the suggestion for solving the problem is recorded in JP Patent Registration the 3946825th, it discloses：In nothing
The method that cyano ethyl compound is prepared as catalysts using Lithium hydrate under water condition.There is record to show：The party
Method suppresses the generation of double (2- cyano ethyls) ethers, and also reduces the coloring caused by acrylonitrile polymerization.
However, Lithium hydrate can not be effectively prevented the polymerization of the nitrile compound with unsaturated bond, and its dissolubility
It is relatively low, therefore there is a problem of increasing the response time.
The content of the invention
Technical problem
The application aims to solve the problem that problem of the prior art, therefore a purpose of the application is to provide a kind of response time
It is short and cause productivity ratio it is excellent, and can with simple method prepare high-purity dinitrile compound method.
Technical scheme
According to the application, there is provided a kind of preparation method of dinitrile compound, wherein, make alcoholic compound with have end position carbon-
The nitrile compound of carbon unsaturated bond reacts in anhydrous conditions, in the course of reaction, the potassium alcohol with 1 to 5 carbon atom
Salt is used as catalyst.
In the present invention, as long as above-mentioned potassium alkoxide C1-C5The compound that alkoxyl is combined with potassium (K), does not just especially limit
System.The example for being suitable for use in the potassium alkoxide of the application method includes, but not limited to Feldalat KM, potassium ethoxide, potassium tert-butoxide and uncle penta
Potassium alcoholate.These potassium alkoxide can be used alone or use as two or more mixture.
The content of potassium alkoxide can change according to the concrete species of the dinitrile compound for being intended to use, for example, potassium alkoxide
Usage amount can be 0.01 to 5 weight portion, based on the alcoholic compound meter of 100 weight portions, but be not limited to the scope.
In the application method, the alcoholic compound for preparing dinitrile compound can be polyhydroxy-alcohol.Alcoholic compound is excellent
Elect dihydroxy alcohol as.Include ethylene glycol, Propylene Glycol, butanediol and penta suitable for the more particularly example of the alcoholic compound of the application
Glycol.These alcoholic compounds can be used alone or use as two or more mixture.
Example suitable for preparing the nitrile compound with end position carbon-to-carbon unsaturated bond of dinitrile compound includes propylene
Nitrile, 3- butene nitriles and allyl acetonitrile.These nitrile compounds can be used alone or use as two or more mixture.
The reaction can be carried out at 20 to 50 DEG C of relatively low temperature.
Beneficial effect
According to the present processes, as reaction is carried out in anhydrous conditions, hence in so that can suppress as by-product
Double (2- cyano ethyls) ethers formation, and the polymerization of the nitrile compound with carbon-to-carbon unsaturated bond can be suppressed, so as to anti-
Only there is coloring.Additionally, the response time is short, hence help to significantly improve productivity ratio.
Description of the drawings
Accompanying drawing explains the application preferred embodiment, and is used to improve to the application together with first disclosure
Technical spirit further understands.However, the application should not be construed as being limited to accompanying drawing.
Fig. 1 is according to embodiment 1 and nuclear magnetic resonance, NMR (NMR) spectrum of the dinitrile compound of preparation.
Fig. 2 is according to embodiment 1 and the gas chromatogram of the dinitrile compound of preparation.
Fig. 3 is according to comparative example 1 and the gas chromatogram of the dinitrile compound of preparation.
Embodiment
Hereinafter, the preferred embodiment of the application is described in detail by referring to the drawings.Before description, it should be understood that saying
Term used in bright book and claims is not limited to the implication of conventional and dictionary, but best based on inventor
Explanation purpose and suitably define the principle of term, the implication and conceptual understanding based on the corresponding technical elements of the application.
The method that the application offer prepares dinitrile compound.The application preparation method is characterised by, alcoholic compound and tool
The nitrile compound for having end position carbon-to-carbon unsaturated bond reacts in anhydrous conditions, and during the course of the reaction using with 1 to 5
The potassium alkoxide of carbon atom is used as catalyst.
Alkali metal hydroxide and organic base are used to prepare dinitrile compound as catalyst.However, these catalyst
Make the nitrile compound with unsaturated bond be polymerized, thus cause the discoloration (color) of reactant.
By contrast, in the application method, the nitrilation with unsaturated bond is not caused using potassium alkoxide as catalyst
The polyreaction of compound, therefore the discoloration of reactant can be avoided.Additionally, the potassium alkoxide of high-dissolvability shortens for needed for dissolving
The time wanted, therefore obtain high productivity ratio.
Additionally, in the application method, being reacted using alcohol potassium salt in anhydrous conditions, therefore do not form any miscellaneous
Matter such that it is able to prepare highly purified dinitrile compound.
It is not particularly limited the species of alcohol potassium salt.For example, alcohol potassium salt can be combined with C for potassium (K)1-C5Anyization of alkoxyl
Compound.Feldalat KM, potassium ethoxide, potassium tert-butoxide and tert-pentyl alcohol are included but is not limited to suitable for the example of the alcohol potassium salt of the application method
Potassium.These Feldalat KMs can be used alone or be used with its two or more mixture, but be not limited to this.
Content for the Feldalat KM of reaction can be according to the specific species of desired dinitrile compound and as reaction
The species and content of the alcoholic compound of thing or the nitrile compound with unsaturated bond and it is suitably selected.For example, Feldalat KM can
To use with 0.01 to 5 weight portion, based on the alcoholic compound meter of 100 weight portions, but the scope is not limited to.If Feldalat KM
Content is less than 0.01 weight portion, then reaction rate is low.Meanwhile, if the content of Feldalat KM is higher than 5 weight portions, which no longer illustrates
As the effect using catalyst, reactivity is improved, and be not easy to after completion of reaction remove catalyst.
In the application method, the alcoholic compound as reactant is the compound with alcohol groups (- OH).Alcoholic compound
It is not particularly limited, as long as which can be used for preparing dinitrile compound.In alcoholic compound the quantity of carbon atom be, for example, 1 to
10, preferably 1 to 5, more preferably 2 to 5, but not limited to this.Alcoholic compound is preferably dihydroxy alcohol.
Ethylene glycol, Propylene Glycol, fourth two are included but is not limited to suitable for the specific example of the alcoholic compound of the application method
Alcohol and pentanediol.These alcoholic compounds can be used alone or use as two or more mixture.
In the application method, the nitrilation with end position carbon-to-carbon unsaturated bond used as other reactant is closed
Thing is：There is nitrile group in molecule one end, and there is carbon-to-carbon unsaturated bond in the other end.For example, nitrile compound can be nitrile
Group is connected to the compound of carbon-to-carbon unsaturated bond by least one alkylidene.With suitable for insatiable hunger used in this application
Acrylonitrile, 3- butene nitriles and allyl acetonitrile are included but is not limited to the specific example of the nitrile compound of key.These nitrile compounds
Can be used alone or use as two or more mixture.
According to the present processes, it is possible to use reactant and catalyst prepare dinitrile compound in simple method.
The embodiment of methods described is more fully described hereinafter.
Add Feldalat KM catalyst in alcoholic compound, and carry out by heat and/or stirring being sufficiently mixed until
Above-mentioned catalyst is completely dissolved.After catalyst dissolution, by undersaturated nitrile compound lentamente Deca and carry out two nitrilations
The generation of compound.After being added dropwise to complete, reactant is completed into dinitrile compound being sufficiently mixed by processes such as stirrings
Reaction of formation.After completion of reaction, the separation of dinitrile compound is carried out using appropriate solvent and filter and be obtained.
The present processes can be prepared at such as 20 to 50 DEG C of relatively low temperature, thus with side simply and readily
Formula prepares dinitrile compound.
Those skilled in the art consider the concrete species of desired dinitrile compound and suitably determine alcoholic compound with tool
The mixing ratio having between the nitrile compound of unsaturated bond.
The application also provides the dinitrile compound prepared by methods described.The dinitrile compound of the application is preferably with two
The compound of individual above ehter bond.Specifically, the application dinitrile compound can be represented by formula 1：
Wherein, R1、R2And R3It is each independently C1-C5Alkylidene or alkenylene, and m is 1 to 5 integer.
More specifically, the dinitrile compound of the application can be selected from, but be not limited to, and 3,5- dioxas-pimelic dinitrile, Isosorbide-5-Nitrae-
Double (cyanoethoxy) butane, double (2- cyano ethyls)-monoformals, double (2- cyano ethyls)-two formals, double (2- cyano group
Ethyl)-three formals, ethylene glycol double (2- cyano ethyls) ether, double (2- (2- cyanoethoxies) ethyl) ethers, 4,7,10,13- tetra-
Oxa- hexadecane dintrile, five oxa- nonadecane -1,14- dintrile of 4,7,10,13,16-, six oxa-s 20 of 3,6,9,12,15,18-
Alkane dintrile, 4,10- dioxas-hendecane dintrile, 1,10- dicyano -3,8- dioxadecanes, 4,10- dioxas-tridecane two
Nitrile and 6,9- dioxas-tetradecane dintrile.
The application also provides the non-aqueous electrolytic solution for lithium secondary battery, and wherein non-aqueous electrolytic solution includes lithium
Salt, organic solvent and the dinitrile compound as additive.
Had the dinitrile compound of ehter bond can be in the cathode surface being made up of lithium-transition metal oxide according to the application
Form complex.The complexing suppresses the Oxidation between electrolyte solution and negative electrode, thus suppresses heating, and prevents
The internal short-circuit for drastically being raised and caused by battery temperature.
There are multiple compounds in non-aqueous electrolytic solution during charging and discharging.Especially, such as HF and PF5It is this kind of
Compound makes non-aqueous electrolytic solution be formed as sour environment.The sour environment accelerates non-aqueous electrolytic solution in cathode surface
Oxidation.According to the application present in the dinitrile compound with ehter bond in oxygen atom (- O-), with non-aqueous electrolytic solution
Such as HF and PF5This kind of compound is combined and the generation of suppression sour environment, it is possible thereby to suppress the oxidation of non-aqueous electrolytic solution
Decomposition reaction.
The dinitrile compound of ehter bond is had according to the application, compared with additive known to other, in terms of battery performance
With improved effect.Specifically, battery can be given with excellent electrochemical properties using the dinitrile compound of the application,
Such as high power capacity retention and improved charging and discharging cycle life.
Lithium salts as electrolyte in the non-aqueous electrolytic solution of the application can be electric comprising lithium secondary battery is generally used for
Any lithium salts in electrolyte solution.For example, the anion of lithium salts can be selected from F-、Cl-、Br-、I-、NO3 -、N(CN)2 -、BF4 -、
ClO4 -、AlO4 -、AlCl4 -、PF6 -、SbF6 -、BF2C2O4 -、BC4O8 -、(CF3)2PF4 -、(CF3)3PF3 -、(CF3)4PF2 -、(CF3)5PF-、(CF3)6P-、CF3SO3 -、C4F9SO3 -、CF3CF2SO3 -、(CF3SO2)2N-、(FSO2)2N-、CF3CF2(CF3)2CO-、
(CF3SO2)2CH-、(SF5)3C-、(CF3SO2)3C-、CF3(CF2)7SO3 -、CF3CO2 -、CH3CO2 -、SCN-(CF3CF2SO2)2N-In
One kind.
The organic solvent being included in the application non-aqueous electrolytic solution can be to be generally used for lithium secondary battery electrolyte
Any solvent in those of solution.The nonrestrictive example of the organic solvent suitable for non-aqueous electrolytic solution include but
It is not limited to ether, ester, amide, linear carbonate and cyclic carbonate salt.These organic solvents can be used alone or with its two kinds with
Upper mixture is used.
Non-aqueous electrolytic solution can include carbonate products, such as cyclic carbonate, linear carbonates or its mixture,
As the representative example of organic solvent.Specifically, cyclic carbonate compound can be selected from ethylene carbonate (ethylene
Carbonate, EC), propylene carbonate (propylene carbonate, PC), 1,2- butylene carbonate, 2,3- carbonic acid are sub-
One kind in butyl ester, 1,2- pentylenes, 2,3- pentylenes, vinylene carbonate, its halogenide or which is two or more
Mixture.Linear carbonate compounds can be selected from, but not limited to, dimethyl carbonate (dimethyl carbonate, DMC),
Diethyl carbonate (diethyl carbonate, DEC), dipropyl carbonate, ethyl methyl carbonate (EMC), methyl propyl ester,
One kind or its two or more mixture in carbonic acid ethylpropyl.
It is height as the ethylene carbonate and propylene carbonate of the cyclic carbonate in above-mentioned carbonic ester system organic solvent
Degree is sticky and with high dielectric constant, they particularly preferably because which can make to be present in electrolyte solution well
Lithium salts separate.More preferably in proper proportions using this kind of cyclic carbonate and the low linear carbonates of viscosity and dielectric constant
The mixture of (such as dimethyl carbonate or diethyl carbonate), because its electrolyte that can be used for preparing with high conductivity is molten
Liquid.
The example of the ether in above-mentioned organic solvent include but is not limited to dimethyl ether, diethyl ether, dipropyl ether, methyl ethyl ether,
Methyl-propyl ether and ethyl propyl ether.These ethers can be used alone or be used with its two or more mixture.
In addition, the example of ester in above-mentioned organic solvent include but is not limited to methyl acetate, ethyl acetate, propyl acetate,
Methyl propionate, ethyl propionate, gamma-butyrolacton, gamma-valerolactone, γ-hexalactone, σ-valerolactone and 6-caprolactone.These esters can be with
It is used alone or is used with its two or more mixture.
The non-aqueous electrolytic solution of the application can be injected into by negative electrode, anode and insert barrier film in-between the electrodes and group
Into electrode assembly, thus prepare lithium secondary battery.Negative electrode, anode and the barrier film of electrode assembly are constituted, can be usual
For prepare lithium secondary battery those.
Hereinafter, the embodiment that will be described in the application.However, the embodiment of the application can be taken
Other modes, scope of the present application should not be construed as limiting to following examples.The embodiment of the application is provided with more complete
The application is explained to the those of ordinary skill in herein described field in ground.
Embodiment 1
The ethylene glycol and 0.2g potassium tert-butoxides as alcoholic compound of 124.2g are put in flask, and are carried out at 40 DEG C
Heating and stirring.The acrylonitrile of 222.8g is dropped to into mixture in 1 hour.
After being added dropwise to complete, continue to be stirred for 4 hours.Mixed with the distilled water extractive reaction of the dichloromethane and 500g of 200g
Compound.Above-mentioned extraction process is repeated once.Dichloromethane solution is then peeled off, and is distilled under reduced pressure, thus
Double (2- cyano ethyls) ethers of water white ethylene glycol are obtained.
Confirm obtained material by NMR for double (2- cyano ethyls) ethers of ethylene glycol.H NMR spectroscopy is shown in Fig. 1.
The purity of obtained material is determined by gas chromatogram (GC).As a result it is shown in Fig. 2.Shown in Fig. 2, ethylene glycol is double
The purity of (2- cyano ethyls) ether is 99% or higher.
Comparative example 1
It is put into 124.2g as the ethylene glycol and 2% sodium hydrate aqueous solution of alcoholic compound in flask, and
Heated at 40 DEG C and stirred to.The acrylonitrile of 222.8g is dropped to into mixture in 1 hour.
After being added dropwise to complete, continue to be stirred for 3 hours.Mixed with the distilled water extractive reaction of the dichloromethane and 500g of 200g
Compound.Above-mentioned extraction process is repeated once.Dichloromethane solution is then peeled off, and is distilled under reduced pressure, thus
Double (2- cyano ethyls) ethers of water white ethylene glycol are obtained.
Obtained purity is determined by gas chromatogram (GC).As a result it is shown in Fig. 3.Shown in Fig. 3, double (the 2- cyano group of ethylene glycol
Ethyl) purity of ether is 79%, and be 21% as double (2- cyano ethyls) ether forming amounts of by-product.
By these results, can confirm that：Reaction in comparative example 1 is carried out under aqueous conditions, and anhydrous
Above-described embodiment 1 that condition is carried out is compared, and defines double (2- cyano ethyls) ethers as by-product, and thus purity is not high.
Comparative example 2
The sodium hydroxide of the ethylene glycol and 0.1g as alcoholic compound of 124.2g is put in flask, and in 40-50
Heated at DEG C and stirred.The acrylonitrile of 222.8g is dropped to into mixture in 2 hours.
Reactant mixture start behind 1 hour from after Deca discoloration, and after the completion of being added dropwise over precipitate one
Rise and be changed into black.After completion of the reaction, if form required product (double (2- cyano ethyls) ethers of ethylene glycol) and gas phase cannot be passed through
Chromatograph determines.
By these results, it can be seen that the polymerization as the acrylonitrile of raw material hinders the formation of required product, and makes
Into there is coloring phenomenon.
Claims (2)
1. a kind of preparation method of dinitrile compound, it is characterised in that make alcoholic compound and there is end position carbon-to-carbon unsaturated bond
Nitrile compound reacts in anhydrous conditions, wherein the nitrile compound with end position carbon-to-carbon unsaturated bond is selected from acrylonitrile, 3-
Any one in butene nitrile, allyl acetonitrile or its two or more mixture,
Wherein alcoholic compound is reacted and is added on the carbon of the end position with the end position carbon of the carbon-to-carbon unsaturated bond of nitrile compound,
In the course of reaction, the alcohol potassium salt with 1 to 5 carbon atom is used as catalyst,
Wherein alcohol potassium salt is selected from potassium tert-butoxide, tert-pentyl alcohol potassium and its mixture,
The alcoholic compound is selected from any one in ethylene glycol, Propylene Glycol, butanediol, pentanediol or its two or more mixing
Thing,
Wherein described reaction is carried out at a temperature of 20 to 40 DEG C.
2. the preparation method of the dinitrile compound described in claim 1, it is characterised in that
The usage amount of the alcohol potassium salt be 0.01 to 5 weight portion, the alcoholic compound meter based on 100 weight portions.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20110024437 | 2011-03-18 | ||
| KR10-2011-0024437 | 2011-03-18 | ||
| KR1020120003863A KR101440529B1 (en) | 2011-03-18 | 2012-01-12 | Method of preparing dinitrile compounds |
| KR10-2012-0003863 | 2012-01-12 | ||
| PCT/KR2012/000485 WO2012128462A1 (en) | 2011-03-18 | 2012-01-19 | Method for preparing a dinitrile compound |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103429566A CN103429566A (en) | 2013-12-04 |
| CN103429566B true CN103429566B (en) | 2017-03-22 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201280014212.4A Active CN103429566B (en) | 2011-03-18 | 2012-01-19 | Method for preparing a dinitrile compound |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US9394242B2 (en) |
| EP (1) | EP2687505B1 (en) |
| JP (1) | JP5802284B2 (en) |
| KR (1) | KR101440529B1 (en) |
| CN (1) | CN103429566B (en) |
| WO (1) | WO2012128462A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103980156B (en) * | 2014-05-22 | 2016-04-06 | 中国科学院福建物质结构研究所 | A kind of preparation method of alkyl diol (two propionitrile base) ether |
| CN105481718A (en) * | 2015-12-07 | 2016-04-13 | 张家港瀚康化工有限公司 | Production method of butenediol bis (propionitrile) ether |
| CN105418456A (en) * | 2015-12-07 | 2016-03-23 | 张家港瀚康化工有限公司 | Preparation method of butanediol bis(propionitrile) ether |
| CN109134309B (en) * | 2018-09-19 | 2020-12-29 | 张家港瀚康化工有限公司 | Method for purifying ethylene glycol bis (propionitrile) ether |
| CN114621117A (en) * | 2022-05-16 | 2022-06-14 | 山东海科新源材料科技股份有限公司 | Method for preparing ethylene glycol bis (propionitrile) ether crude product by anhydrous method |
| CN115322119B (en) * | 2022-07-29 | 2023-09-29 | 抚顺顺能化工有限公司 | Preparation method of ethylene glycol bis (propionitrile) ether |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263716A (en) * | 2004-03-19 | 2005-09-29 | Mitsubishi Chemicals Corp | Method for producing cyanoalkoxy compound |
| JP2005263717A (en) * | 2004-03-19 | 2005-09-29 | Mitsubishi Chemicals Corp | Method for producing cyanoalkoxy compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US2977337A (en) * | 1956-03-21 | 1961-03-28 | American Cyanamid Co | Cyanoethylated polyacrylonitrile compositions |
| US2941990A (en) * | 1957-07-15 | 1960-06-21 | American Cyanamid Co | Cyanoethylated polymers |
| JPS554380A (en) * | 1978-06-16 | 1980-01-12 | Suntech | Continuous cyanoethylation |
| JP3946825B2 (en) | 1997-09-10 | 2007-07-18 | サンスター技研株式会社 | Method for producing cyanoethyl compound for electrolyte of lithium or lithium ion secondary battery |
| WO2009152392A2 (en) * | 2008-06-11 | 2009-12-17 | University Of Toledo | Muscarinic agonists for neurological disorders and methods of making the same |
| JP2013075837A (en) * | 2011-09-29 | 2013-04-25 | Fujifilm Corp | Manufacturing method for nitrile compound |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2005263716A (en) * | 2004-03-19 | 2005-09-29 | Mitsubishi Chemicals Corp | Method for producing cyanoalkoxy compound |
| JP2005263717A (en) * | 2004-03-19 | 2005-09-29 | Mitsubishi Chemicals Corp | Method for producing cyanoalkoxy compound |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5802284B2 (en) | 2015-10-28 |
| EP2687505B1 (en) | 2018-04-04 |
| KR20120106546A (en) | 2012-09-26 |
| US20140018567A1 (en) | 2014-01-16 |
| KR101440529B1 (en) | 2014-09-17 |
| EP2687505A4 (en) | 2014-10-08 |
| CN103429566A (en) | 2013-12-04 |
| US9394242B2 (en) | 2016-07-19 |
| EP2687505A1 (en) | 2014-01-22 |
| WO2012128462A1 (en) | 2012-09-27 |
| JP2014519473A (en) | 2014-08-14 |
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Effective date of registration: 20211217 Address after: Seoul, South Kerean Patentee after: LG Energy Solution,Ltd. Address before: Seoul, South Kerean Patentee before: LG CHEM, Ltd. |